Phosphor, its preparation method and light emitting devices using the same

ABSTRACT

A phosphor can be excited by UV, purple or blue light LED, its preparation method, and light emitting devices incorporating the same. The phosphor contains rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. Its General formula of is aLn 2 O 3 .MO.bM′ 2 O 3 .fSiO 2 .cAX e :dR, wherein Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm; M is at least one metal element selected from a group consisting of Ca, Sr and Ba; M′ is at least one metal element selected from Al and Ga; A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba; X is at least one element selected from F and Cl; R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn; 0.01≦a≦2, 0.35≦b≦4, 0.01≦c≦1, 0.01≦d≦0.3, 0.01≦f≦3, 0.6≦e≦2.4. The phosphor has broad emitting range, high efficiency, better uniformity and stability. A light emitting device is obtained by incorporating the phosphor into a UV, purple or blue light emitting device.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application filed under 35 U.S.C. §111(a), claiming the benefit under 35 U.S.C. §120 and §365(c) of a PCT International Application Number PCT/CN2007/000852, filed Mar. 16, 2007, it being further noted that foreign priority benefit is based upon Chinese Patent Application 200610065812.X, filed Mar. 24, 2006 in the State Intellectual Property Office of P.R. China, the disclosures of which are thereby incorporated by reference.

FIELDS OF THE INVENTION

The present invention relates to a phosphor that can be excited by ultraviolet, purple or blue LEDs, the preparation method thereof, and light emitting devices using the same.

BACKGROUND OF THE INVENTION

Light emitting diodes (“LEDs”) have attracted much attention due to many advantages, such as small volume, low power consumption, long lifetime, fast-response, environmental friendliness, and high reliability etc. They are used widely in indicating lamps, decorating lamps, signal lamps etc. It can be looked forward to the coming future that LEDs will access into general lighting field with the faster and advanced developments.

Generally, there are two ways to generate white LED: one way is to combine the red, green and blue LEDs to get white light; the other way is to excite phosphors with LED to obtain white light. According to the difference in phosphors, the latter approach includes three routes: matching yellow phosphor with blue LED, matching green and red phosphors with blue LED, or matching red, green and blue phosphors with purple or UV LEDs.

As for current LED techniques, white LEDs are preferred to be generated by incorporating blue LED with YAG (yttrium aluminum garnet) yellow phosphor. In the Chinese patent CN97196762, this phosphor is reported in details. However, due to the characteristics of the phosphor, the luminous efficiency of white LEDs using this YAG phosphor is not yet adequate at present, and it is not applicable in general lighting field by taking into account the energy-saving. Therefore, the studies on novel phosphors with good luminescence performance are focused by many researchers from all over the world.

A silicate-borate phosphor represented by the formula (Y,La)_(1-x-y-z)Ce_(x)Gd_(y)Tb_(z)(Mg,Zn,Gd)_(1-p)Mn_(p)B_(5-q-s)(Al,Ga)_(q)X_(s)O₁₀ has been reported in the German patent DE19730005. Phosphors comprising silicon, disclosed in British patents GB1334838, GB1326868 and GB1379949, with emission main peaks at 370-430 nm, are employed as cathode ray exciting phosphors. An alkaline-earth silicate phosphor that can be excited by blue light to generate yellow light, with similar performance as that of the YAG phosphor, has been developed by Barry (J. Electrochem. Soc., 1968, 115: 1181-1184), and has been described in white LED in U.S. Patent Publication US20040051111.

SUMMARY OF THE INVENTION

One aspect of the present invention is to provide a phosphor that possesses desirable chemical stability, high luminous efficiency and can be excited efficiently by ultraviolet, purple or blue LED's.

Another aspect of the present invention is to provide a preparation method for the phosphor mentioned above.

Still another aspect of the present invention is to provide a light emitting device that incorporates the above mentioned phosphor.

A phosphor according to one aspect of the invention contains, for example, rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. Rare earth refers to “rare earth elements” or “rare earth metals,” and hereinafter, the expression “rare earth” will be used. The rare earth is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm, as well as at least one metal element selected from a group consisting of Ce, Eu and Tb. The alkaline-earth metal is at least one metal element selected from a group consisting of Mg, Ca, Sr and Ba. The halogen is at least one element selected from F and Cl. The phosphor according to one aspect of the present invention possesses high conversion efficiency, and can be used to produce white LED with high luminous efficiency.

As one embodiment, the phosphor can be represented by the general formula of aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;

M is at least one metal element selected from a group consisting of Ca, Sr and Ba;

M′ is at least one metal element selected from Al and Ga;

A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;

X is at least one element selected from F and Cl;

R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;

0.01≦a≦2;

0.35≦b≦4;

0.01≦c≦1;

0.01≦d≦0.3;

0.01≦f≦3; and

0.6≦e≦2.4.

The phosphor according to the present invention has excellent luminescent properties such as wide exciting wavelength scope, efficient emitting transition and chemical stability, and can be excited by ultraviolet, purple or blue LED. New light emitting devices can be obtained by incorporating the phosphor into the LED.

A preparation method for the phosphor mentioned above includes the following:

(1) According to the general formula: aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;

M is at least one metal element selected from a group consisting of Ca, Sr and Ba;

M′ is at least one metal element selected from Al and Ga;

A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;

X is at least one element selected from F and Cl;

R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;

0.01≦a≦2;

0.35≦b≦4;

0.01≦c≦1;

0.01≦d≦0.3;

0.01≦f≦3; and

0.6≦e≦2.4;

weighing elementary substance or compounds or salts of Ln, M, M′, halide of A, and compounds or salts of R and Si as raw materials based on the stoichiometric ratio;

adding at the same time, excess quantity of SiO₂ and/or AXe as flux into the above raw materials, then mixing and grinding together to form a mixture.

(2) baking the mixture at high temperature under reducing atmosphere to form a baked product.

(3) Carrying out a post-treatment to the baked product to obtain the phosphor of the present invention.

According to (1) above, the compounds of Ln, M, M′, A, R and Si are selected from oxide, hydroxide etc.; the salts are selected from the corresponding carbonate, nitrate, organic salt etc.

According to (1) above, the amount of the flux is 0.001-20 wt % by weight of the total phosphor.

According to (1) above, the starting materials can be mixed and grinded in alcohol, acetone or water.

According to (2) above, the operation of baking can be carried out once, twice or more.

According to (2) above, the temperature of baking is at 500˜1600° C.

According to (2) above, each baking operation should last for 0.5˜15 h.

According to (3) above, the post-treatment includes grinding, air flow crushing, washing, sifting, drying and grading, etc.

According to (3) above, the washing step in the post-treatment can be done by using acid solution, alkali solution or water.

According to (3) above, the grading step in the post-treatment can be carried out with at least one method selected from a group consisting of sedimentation method, sieving method, hydraulic classification and air flow grading.

It is easily found that the above preparation method of the present phosphor is advantageous for being very simple, involving no pollution and having low cost. Also, this phosphor can be excited by UV, purple or blue light to emit broadband visible light with wavelengths peaking at 500-600 nm and having full width at half maximum (“FWHM”) beyond 30 nm. That is to say, the phosphor of the present invention can match UV, purple or blue LED, and can be implanted directly or along with other phosphors into LEDs to produce white or color light emitting devices.

In accordance with an aspect of the present invention, a light emitting device can be produced by combining the present phosphor with at least a kind of LED, such as UV, purple or blue LED. The phosphor contains rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. The rare earth is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm as well as at least one metal element selected from a group consisting of Ce, Eu and Tb The alkaline-earth metal is at least one metal element selected from a group consisting of Mg, Ca, Sr and Ba. The halogen is at least one element selected from F and Cl.

The phosphor can be represented by the general formula of aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;

M is at least one metal element selected from a group consisting of Ca, Sr and Ba;

M′ is at least one metal element selected from Al and Ga;

A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;

X is at least one element selected from F and Cl;

R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;

0.01≦a≦2,

0.35≦b≦4,

0.01≦c≦1,

0.01≦d≦0.3,

0.01≦f≦3, and

0.6≦e≦2.4.

The above-described phosphor of the present invention has excellent luminescent properties and stability with novel composition.

The preparation method for the phosphor is simple, involving no pollution and having lower cost.

A light emitting device is obtained by incorporating the phosphor into an LED, which has long lifetime and high luminous efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the excitation spectrum of Example 1;

FIG. 2 shows the emission spectrum of the Example 1.

DESCRIPTION OF THE EXAMPLES

In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that the same are intended only as illustrative and in nowise limitative. The scope of protection of this invention will be further embodied in the claims.

Example 1

In this example, the formula of the phosphor is verified as 1.47Y₂O₃.BaO.2.48Al₂O₃.1.03SiO₂.0.03BaF₂:0.03Ce,0.01Eu. Raw materials Y₂O₃(4N), BaO(4N), Al₂O₃(4N), CeO₂(4N), Eu₂O₃(4N), SiO₂(4N), BaF₂(AR), are weighed with appropriate stoichiometric ratio. SiO₂ and BaF₂ act as both reactant and flux. The amount of flux is 18 wt % by weight of above raw materials, and the weight ratio of the flux, SiO₂ and BaF₂, is 1:1. Mixing and grinding these materials, and then baking them at 1450° C. for 3 hours under reducing atmosphere. After crushing, washing, sifting, drying and sieving, the phosphor can be obtained. As shown in FIG. 1, the phosphor can be excited by 350-480 nm and emit 544 nm yellow light.

Example 2

In this example, the formula of the phosphor is verified as 1.47Y₂O₃.BaO.2.47Al₂O₃.1.03SiO₂.0.06BaF₂:0.04Ce,0.03Eu. Raw materials Y₂O₃(4N), BaO(4N), Al₂O₃(4N), CeO₂(4N), Eu₂O₃(4N), SiO₂(4N), BaF₂(AR), are weighed with appropriate stoichiometric ratio. SiO₂ and BaF₂ act as both reactant and flux. The amount of flux is 10 wt % by weight of above raw materials, wherein the weight ratio of SiO₂ and BaF₂ is 1:1. The preparation method is similar as that of Example 1 but with different roasting times, temperature and period and taking crushing and sifting during the intermission of two-stage baking, namely, first, baking at 1400° C. for 2 hours in reducing atmosphere, then crushing, sieving and baking at 1550° C. for 2 hours in reducing atmosphere. After crushing, washing, sieving and drying, the phosphor can be obtained. The relative emission intensity is shown in Table 1.

Examples 3-72

In these examples, the formulae of the phosphors are listed in Table 1. In EXAMPLES 3-72, raw materials: oxides of Ln, M and M′, halide of A (AXe), oxides of R, and oxides of Si (SiO₂), are weighed in accordance with the stoichiometric ratio of the formula of each embodiment. The oxides of Si and the halide of A may act as both reactant and flux. The amount of flux is 10 wt % by weight of above raw materials, wherein the weight ratio of the flux, oxides of Si and halide of A, is 1:1. The preparation step is similar as that of EXAMPLE 2, namely, first, baking at 1400° C. for 2 hours in reducing atmosphere, then crushing, sieving and baking at 1550° C. for 2 hours in reducing atmosphere. After crushing, washing, sieving and drying, the phosphor can be obtained. The relative emission intensity is showed in Table 1.

TABLE 1 The formulae and emission intensity of EXAMPLES 1-72 Relative Intensity (%) Excited by Excited by EXAMPLES Formula 330 nm 460 nm 1 1.47Y₂O₃•BaO•2.48Al₂O₃•1.03SiO₂•0.03BaF₂:0.03Ce, 0.01Eu 100 100 2 1.47Y₂O₃•BaO•2.47Al₂O₃•1.03SiO₂•0.06BaF₂:0.04Ce, 0.03Eu 105 106 3 Y₂O₃•0.48Sm₂O₃•BaO•2.45Al₂O₃•1.09SiO₂•0.06BaF₂:0.03Ce, 0.04Eu 96 97 4 La₂O₃•0.22Gd₂O₃•0.25Sm₂O₃•BaO•2.44Al₂O₃•1.12SiO₂•0.06BaF₂:0.06Ce, 0.01Eu, 0.001Tb 94 94 5 2.0Y₂O₃•BaO•1.0Al₂O₃•0.05Ga₂O₃•2.5SiO₂•0.36BaF₂:0.07Ce, 0.03Eu, 0.001Tb 90 91 6 1.91Y₂O₃•BaO•2.0Al₂O₃•1.06SiO₂•0.1LiF:0.09Ce, 0.02Eu, 0.001Tb 104 106 7 1.34Pr₂O₃•BaO•2.5Al₂O₃•1.09SiO₂•0.16LiCl:0.01Ce, 0.08Eu, 0.002Tb 108 110 8 0.818Y₂O₃•BaO•3.0Al₂O₃•1.12SiO₂•0.2NaF:0.1Ce, 0.04Eu, 0.003Tb 106 105 9 0.297Y₂O₃•BaO•3.5Al₂O₃•1.15SiO₂•0.2NaCl:0.12Ce, 0.02Eu, 0.004Tb 103 104 10 0.01Y₂O₃•BaO•4.0Al₂O₃•0.01SiO₂•0.918KF:0.02Ce, 0.1Eu, 0.001Tb 112 115 11 1.473Nd₂O₃•BaO•2.79Al₂O₃•0.05SiO₂•0.37KCl:0.02Ce, 0.11Eu, 0.002Tb 91 92 12 1.471Y₂O₃•BaO•2.81Al₂O₃•0.1SiO₂•0.28MgF₂:0.1Ce, 0.12Eu, 0.003Mn 90 89 13 1.472Y₂O₃•BaO•2.61Al₂O₃•0.5SiO₂•0.28MgCl₂:0.13Ce, 0.01Eu, 0.001Mn 82 84 14 1.482Y₂O₃•BaO•2.215Al₂O₃•1.0SiO₂•0.57CaF₂:0.01Ce, 0.12Eu, 0.004Mn 94 95 15 1.133Ho₂O₃•BaO•2.2Al₂O₃•2.0SiO₂•0.3CaCl₂:0.1Ce, 0.02Eu, 0.001Tb 97 96 16 0.8Y₂O₃•BaO•0.42Al₂O₃•3.0SiO₂•0.16SrF₂:0.01Ce, 0.1Eu, 0.003Tb 89 92 17 1.47Y₂O₃•BaO•2.42Al₂O₃•SiO₂•0.16SrCl₂:0.1Ce, 0.04Eu 88 89 18 Yb₂O₃•0.47Gd₂O₃•BaO•2.24Al₂O₃•1.36SiO₂•0.16LiF:0.13Ce, 0.01Eu 92 93 19 Y₂O₃•0.44Gd₂O₃•BaO•2.25Al₂O₃•1.39SiO₂•0.16LiCl:0.08Ce, 0.09Eu 91 93 20 Y₂O₃•0.44Gd₂O₃•BaO•2.21Al₂O₃•1.42SiO₂•0.16NaF:0.09Ce, 0.02Eu 94 95 21 Y₂O₃•0.41Gd₂O₃•BaO•2.195Al₂O₃•1.45SiO₂•0.16NaCl:0.15Ce, 0.13Eu 88 89 22 Y₂O₃•0.41Gd₂O₃•BaO•2.18Al₂O₃•1.48SiO₂•0.16KF:0.01Ce, 0.01Eu 91 92 23 Y₂O₃•0.38Gd₂O₃•CaO•2.42Al₂O₃•1.48SiO₂•0.16KCl:0.03Ce, 0.03Eu 86 87 24 Y₂O₃•0.38Gd₂O₃•CaO•2.165Al₂O₃•1.51SiO₂•0.16MgF₂:0.08Ce, 0.002Tb 94 95 25 Y₂O₃•0.35Sc₂O₃•CaO•2.15Al₂O₃•1.54SiO₂•0.16MgCl₂:0.02Ce, 0.005Tb 89 91 26 Y₂O₃•0.35Gd₂O₃•CaO•2.3Al₂O₃•1.12SiO₂•0.16CaF₂:0.04Ce, 0.001Tb 102 101 27 Y₂O₃•0.32Gd₂O₃•CaO•2.135Al₂O₃•1.57SiO₂•0.16CaCl₂:0.07Ce, 0.08Eu 92 93 28 Y₂O₃•0.32La₂O₃•CaO•2.12Al₂O₃•1.6SiO₂•0.16SrF₂:0.02Ce, 0.12Eu 89 90 29 Y₂O₃•0.29Gd₂O₃•CaO•2.105Al₂O₃•1.63SiO₂•0.16SrCl₂:0.14Ce, 0.02Eu 87 88 30 Y₂O₃•0.29Pr₂O₃•CaO•2.09Al₂O₃•1.66SiO₂•0.16BaCl₂:0.02Ce, 0.02Eu 93 94 31 Y₂O₃•0.26Sm₂O₃•CaO•2.125Al₂O₃•1.74SiO₂•0.01LiF:0.06Ce, 0.06Eu 100 101 32 Y₂O₃•0.26Sm₂O₃•CaO•2.11Al₂O₃•1.75SiO₂•0.03LiCl:0.09Ce, 0.08Eu 98 100 33 Y₂O₃•0.23Sm₂O₃•CaO•2.095Al₂O₃•1.75SiO₂•0.06NaF:0.06Ce, 0.07Eu 102 103 34 Y₂O₃•0.23Sm₂O₃•CaO•2.08Al₂O₃•1.74SiO₂•0.1NaCl:0.05Ce, 0.08Eu 96 97 35 Y₂O₃•0.2Sm₂O₃•CaO•2.065Al₂O₃•1.67SiO₂•0.2KF:0.16Ce, 0.13Eu 97 98 36 Y₂O₃•0.2Sm₂O₃•CaO•2.05Al₂O₃•1.6SiO₂•0.3KCl:0.15Ce, 0.13Eu 101 102 37 Y₂O₃•0.47Sm₂O₃•CaO•2.23Al₂O₃•0.9SiO₂•0.4MgF₂:0.13Ce, 0.1Eu 96 97 38 Y₂O₃•0.47Nd₂O₃•CaO•2.035Al₂O₃•1.43SiO₂•0.5MgCl₂:0.04Ce, 0.04Eu 96 95 39 Y₂O₃•0.47Sm₂O₃•CaO•2.02Al₂O₃•1.36SiO₂•0.6CaF₂:0.02Ce, 0.03Eu 91 92 40 Y₂O₃•0.47Sm₂O₃•CaO•2.005Al₂O₃•1.29SiO₂•0.7CaCl₂:0.12Ce, 0.03Eu 86 87 41 Y₂O₃•0.47Sm₂O₃•CaO•1.99Al₂O₃•1.22SiO₂•0.8SrF₂:0.13Ce, 0.04Eu 88 89 42 Y₂O₃•0.47Sm₂O₃•CaO•2.46Al₂O₃•0.18SiO₂•0.9SrCl₂:0.14Ce, 0.05Eu 85 86 43 Y₂O₃•0.47Ho₂O₃•CaO•2.45Al₂O₃•0.1SiO₂•1.0BaCl₂:0.06Ce, 0.06Eu 96 97 44 1.47Y₂O₃•CaO•2.39Al₂O₃•0.05Ga₂O₃•1.08SiO₂•0.1LiF:0.08Ce, 0.05Eu 99 100 45 0.01Y₂O₃•CaO•3.84Al₂O₃•0.05Ga₂O₃•1.00SiO₂•0.2LiCl:0.11Ce, 0.02Eu 103 102 46 0.05Yb₂O₃•CaO•3.36Al₂O₃•0.05Ga₂O₃•1.3SiO₂•0.3NaF:0.1Ce, 0.05Eu 108 107 47 0.1Y₂O₃•CaO•3.74Al₂O₃•0.05Ga₂O₃•0.82SiO₂•0.4NaCl:0.1Ce, 0.03Eu 93 94 48 0.5Y₂O₃•CaO•3.33Al₂O₃•0.05Ga₂O₃•0.74SiO₂•0.5KF:0.09Ce, 0.02Eu 90 91 49 1.0Y₂O₃•CaO•2.82Al₂O₃•0.05Ga₂O₃•0.66SiO₂0.6KCl:0.08Ce 85 86 50 2.0Y₂O₃•CaO•1.81Al₂O₃•0.05Ga₂O₃•0.55SiO₂•0.7MgF₂:0.1Eu 96 97 51 0.01Sc₂O₃•SrO•3.79Al₂O₃•0.05Ga₂O₃•0.44SiO₂•0.8MgCl₂:0.007Ce, 0.01Eu 100 100 52 0.05Y₂O₃•SrO•3.74Al₂O₃•0.05Ga₂O₃•0.36SiO₂•0.9CaF₂:0.06Ce, 0.04Eu 93 92 53 0.1Y₂O₃•SrO•3.68Al₂O₃•0.05Ga₂O₃•0.28SiO₂•1.0CaCl₂:0.06Ce, 0.03Eu 96 97 54 0.5Y₂O₃•SrO•3.27Al₂O₃•0.05Ga₂O₃•1.2SiO₂•0.1SrF₂:0.07Ce, 0.04Eu 94 94 55 1.0La₂O₃•SrO•2.76Al₂O₃•0.05Ga₂O₃•1.12SiO₂•0.2SrCl₂:0.09Ce, 0.03Eu 90 91 56 2.0Y₂O₃•SrO•1.75Al₂O₃•0.05Ga₂O₃•1.04SiO₂•0.3BaCl₂:0.1Ce, 0.1Eu 105 106 57 0.47Pr₂O₃•0.5Gd₂O₃•0.5Sm₂O₃•SrO•2.3Al₂O₃•1.34SiO₂•0.06BaF₂:0.1Ce, 0.11Eu 90 90 58 0.47Y₂O₃•Gd₂O₃•SrO•2.29Al₂O₃•1.36SiO₂•0.06BaF₂:0.07Ce, 0.02Eu 89 88 59 0.47Y₂O₃•Gd₂O₃•SrO•2.23Al₂O₃•1.38SiO₂0.12LiF:0.12Ce, 0.02Eu 87 86 60 0.47Nd₂O₃•Gd₂O₃•SrO•2.22Al₂O₃•1.4SiO₂•0.12LiCl:0.02Ce, 0.11Eu 86 87 61 0.44Y₂O₃•Gd₂O₃•SrO•2.21Al₂O₃•1.42SiO₂•0.12NaF:0.02Ce, 0.02Eu 87 85 62 0.44Y₂O₃•Gd₂O₃•SrO•2.2Al₂O₃•1.44SiO₂•0.12NaCl:0.08Ce, 0.08Eu 85 84 63 0.41Y₂O₃•Gd₂O₃•SrO•2.19Al₂O₃•1.43SiO₂•0.12KF:0.07Ce, 0.01Eu 83 84 64 0.41Y₂O₃•Gd₂O₃•SrO•2.42Al₂O₃•1.18SiO₂•0.12KCl:0.01Ce, 0.03Eu 83 83 65 0.38Y₂O₃•Gd₂O₃•SrO•2.19Al₂O₃•1.46SiO₂•0.06MgF₂:0.08Ce, 0.10Eu 89 91 66 0.38Y₂O₃•Gd₂O₃•SrO•2.18Al₂O₃•1.48SiO₂•0.06MgCl₂:0.1Ce, 0.1Eu, 0.1Tb 88 87 67 0.35Y₂O₃•Gd₂O₃•SrO•1.46Al₂O₃•1.96SiO₂•0.06CaF₂:0.16Ce 105 104 68 0.35Pr₂O₃•Gd₂O₃•SrO•2.17Al₂O₃•1.5SiO₂•0.06CaCl₂:0.12Ce, 0.12Eu 81 84 69 0.32Y₂O₃•Gd₂O₃•SrO•2.12Al₂O₃•1.6SiO₂•0.06SrF₂:0.12Ce, 0.10Eu 82 83 70 0.32Y₂O₃•Gd₂O₃•SrO•2.07Al₂O₃•1.7SiO₂•0.06SrCl₂:0.08Ce, 0.12Eu 78 79 71 0.29Y₂O₃•Gd₂O₃•SrO•2.02Al₂O₃•1.8SiO₂•0.06BaF₂:0.06Ce, 0.10Eu 80 78 72 0.29Nd₂O₃•Gd₂O₃•SrO•1.97Al₂O₃•1.9SiO₂•0.06BaCl₂:0.08Ce, 0.10Eu 86 84

Example 73

White light emitting device can be obtained by incorporating the phosphor of EXAMPLE 1 into a blue light LED. The phosphor powder of EXAMPLE 1 is firstly slurried, and then coated on a GaInN LED chip. After welding circuit and packaging, a white light emitting device is produced.

INDUSTRIAL APPLICABILITY

The above-described phosphor has broad emitting range, high efficiency, better uniformity and stability. The production method is simple, no pollution and a lower cost. A light emitting device can be obtained by incorporating this phosphor into a UV, purple or blue light emitting device. 

1. A phosphor represented by a general formula of: aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm; M is at least one metal element selected from a group consisting of Ca, Sr and Ba; M′ is at least one metal element selected from Al and Ga; A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba; X is at least one element selected from F and Cl; R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn; 0.01≦a≦2; 0.35≦b≦4; 0.01≦c≦1, 0.01≦d≦0.3; 0.01≦f≦3; and 0.6≦e≦2.4, wherein the phosphor is a member selected from the group consisting of: 1.47Y₂O₃.BaO.2.48Al₂O₃.1.03SiO₂.0.03BaF₂:0.03Ce,0.01Eu 1.47Y₂O₃.BaO.2.47Al₂O₃.1.03SiO₂.0.06BaF₂:0.04Ce,0.03Eu Y₂O₃.0.48Sm₂O₃.BaO.2.45Al₂O₃.1.09SiO₂.0.06BaF₂:0.03Ce,0.04Eu La₂O₃.0.22Gd₂O₃.0.25Sm₂O₃.BaO.2.44Al₂O₃.1.12SiO₂.0.06BaF₂:0.06Ce,0.01Eu,0.001Tb 2.0Y₂O₃.BaO.1.0Al₂O₃.0.05Ga₂O₃.2.5SiO₂.0.36BaF₂:0.07Ce,0.03Eu,0.001Tb 1.91Y₂O₃.BaO.2.01Al₂O₃.1.06SiO₂.0.1LiF:0.09Ce,0.02Eu,0.001Tb 1.34Pr₂O₃.BaO.2.5Al₂O₃.1.09SiO₂.0.16LiCl:0.01Ce,0.08Eu,0.002Tb 0.818Y₂O₃.BaO.3.0Al₂O₃.1.12SiO₂.0.2NaF:0.1Ce,0.04Eu,0.003Tb 0.297Y₂O₃.BaO.3.5Al₂O₃.1.15SiO₂.0.2NaCl:0.12Ce,0.02Eu,0.004Tb 0.01Y₂O₃.BaO.4.0Al₂O₃.0.01SiO₂.0.918KF:0.02Ce,0.1Eu,0.001Tb 1.473Nd₂O₃.BaO.2.79Al₂O₃.0.05SiO₂.0.37KCl:0.02Ce,0.11Eu,0.002Tb 1.471Y₂O₃.BaO.2.81Al₂O₃.0.1SiO₂.0.28MgF₂:0.1Ce,0.12Eu,0.003Mn 1.472Y₂O₃.BaO.2.61Al₂O₃.0.5SiO₂.0.28MgCl₂:0.13Ce,0.01Eu,0.001 Mn 1.482Y₂O₃.BaO.2.215Al₂O₃.1.0SiO₂.0.57CaF₂:0.01Ce,0.12Eu,0.004Mn 1.133Ho₂O₃.BaO.2.2Al₂O₃.2.0SiO₂.0.3CaCl₂:0.1Ce,0.02Eu,0.001Tb 0.8Y₂O₃.BaO.0.42Al₂O₃.3.0SiO₂.0.16SrF₂:0.01Ce,0.1Eu,0.003Tb 1.47Y₂O₃.BaO.2.42Al₂O₃SiO₂.0.16SrCl₂:0.1Ce,0.04Eu Yb₂O₃.0.47Gd₂O₃.BaO.2.24Al₂O₃.1.36SiO₂.0.16LiF:0.13Ce,0.01Eu Y₂O₃.0.44Gd₂O₃.BaO.2.25Al₂O₃.1.39SiO₂.0.16LiCl:0.08Ce,0.09Eu Y₂O₃.0.44Gd₂O₃.BaO.2.21Al₂O₃.1.42SiO₂.0.16NaF:0.09Ce,0.02Eu Y₂O₃.0.41Gd₂O₃.BaO.2.195Al₂O₃.1.45SiO₂.0.16NaCl:0.15Ce,0.13Eu Y₂O₃.0.41Gd₂O₃.BaO.2.18Al₂O₃.1.48SiO₂.0.16KF:0.01Ce,0.01Eu Y₂O₃.0.38Gd₂O₃.CaO.2.42Al₂O₃.1.48SiO₂.0.16KCl:0.03Ce,0.03Eu Y₂O₃.0.38Gd₂O₃.CaO.2.165Al₂O₃.1.51SiO₂.0.16MgF₂:0.08Ce,0.002Tb Y₂O₃.0.35Sc₂O₃.CaO.2.15Al₂O₃.1.54SiO₂.0.16MgCl₂:0.02Ce,0.005Tb Y₂O₃.0.35Gd₂O₃.CaO.2.3Al₂O₃.1.12SiO₂.0.16CaF₂:0.04Ce,0.001Tb Y₂O₃.0.32Gd₂O₃.CaO.2.135Al₂O₃.1.57SiO₂.0.16CaCl₂:0.07Ce,0.08Eu Y₂O₃.0.32La₂O₃.CaO.2.12Al₂O₃.1.6SiO₂.0.16SrF₂:0.02Ce,0.12Eu Y₂O₃.0.29Gd₂O₃CaO.2.105Al₂O₃.1.63SiO₂.0.16SrCl₂:0.14Ce,0.02Eu Y₂O₃.0.29Pr₂O₃CaO.2.09Al₂O₃.1.66SiO₂.0.16BaCl₂:0.02Ce,0.02Eu Y₂O₃.0.26Sm₂O₃.CaO.2.125Al₂O₃.1.74SiO₂.0.01LiF:0.06Ce,0.06Eu Y₂O₃.0.26Sm₂O₃.CaO.2.11Al₂O₃.1.75SiO₂.0.03LiCl:0.09Ce,0.08Eu Y₂O₃.0.23Sm₂O₃.CaO.2.095Al₂O₃.1.75SiO₂.0.06NaF:0.06Ce,0.07Eu Y₂O₃.0.23Sm₂O₃.CaO.2.08Al₂O₃.1.74SiO₂.0.1NaCl:0.05Ce,0.08Eu Y₂O₃.0.2Sm₂O₃.CaO.2.065Al₂O₃.1.67SiO₂.0.2KF:0.16Ce,0.13Eu Y₂O₃.0.2Sm₂O₃.CaO.2.05Al₂O₃.1.6SiO₂.0.3KCl:0.15Ce,0.13Eu Y₂O₃.0.47Sm₂O₃.CaO.2.23Al₂O₃.0.9SiO₂.0.4MgF₂:0.13Ce,0.1Eu Y₂O₃.0.47Nd₂O₃.CaO.2.035Al₂O₃.1.43SiO₂.0.5MgCl₂:0.04Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.02Al₂O₃.1.36SiO₂.0.6CaF₂:0.02Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.2.005Al₂O₃.1.29SiO₂.0.7CaCl₂:0.12Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.1.99Al₂O₃.1.22SiO₂.0.8SrF₂:0.13Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.46Al₂O₃.0.18SiO₂.0.9SrCl₂:0.14Ce,0.05Eu Y₂O₃.0.47Ho₂O₃.CaO.2.45Al₂O₃.0.1SiO₂.1.0BaCl₂:0.06Ce,0.06Eu 1.47Y₂O₃.CaO.2.39Al₂O₃.0.05Ga₂O₃.1.08SiO₂.0.1LiF:0.08Ce,0.05Eu 0.01Y₂O₃CaO.3.84Al₂O₃.0.05Ga₂O₃.1.00SiO₂.0.2LiCl:0.11Ce,0.02Eu 0.05Yb₂O₃CaO.3.36Al₂O₃.0.05Ga₂O₃.1.3SiO₂.0.3NaF:0.1Ce,0.05Eu 0.1Y₂O₃CaO.3.74Al₂O₃.0.05Ga₂O₃.0.82SiO₂.0.4NaCl:0.1Ce,0.03Eu 0.5Y₂O₃CaO.3.33Al₂O₃.0.05Ga₂O₃.0.74SiO₂.0.5KF:0.09Ce,0.02Eu 1.0Y₂O₃CaO.2.82Al₂O₃.0.05Ga₂O₃.0.66SiO₂.0.6KCl:0.08Ce 2.0Y₂O₃CaO.1.81Al₂O₃.0.05Ga₂O₃.0.55SiO₂.0.7MgF₂:0.1Eu 0.01Sc₂O₃.SrO.3.79Al₂O₃.0.05Ga₂O₃.0.44SiO₂.0.8MgCl₂:0.007Ce,0.01Eu 0.05Y₂O₃.SrO.3.74Al₂O₃.0.05Ga₂O₃.0.36SiO₂.0.9CaF₂:0.06Ce,0.04Eu 0.1Y₂O₃.SrO.3.68Al₂O₃.0.05Ga₂O₃.0.28SiO₂.1.0CaCl₂:0.06Ce,0.03Eu 0.5Y₂O₃.SrO.3.27Al₂O₃.0.05Ga₂O₃.1.2SiO₂.0.1SrF₂:0.007Ce,0.04Eu 1.0La₂O₃.SrO.2.76Al₂O₃.0.05Ga₂O₃.1.12SiO₂.0.2SrCl₂:0.09Ce,0.03Eu 2.0Y₂O₃.SrO.1.75Al₂O₃.0.05Ga₂O₃.1.04SiO₂.0.3BaCl₂:0.1Ce,0.1Eu 0.47Pr₂O₃.0.5Gd₂O₃.0.5Sm₂O₃.SrO.2.3Al₂O₃.1.34SiO₂.0.06BaF₂:0.1Ce,0.11Eu 0.47Y₂O₃Gd₂O₃.SrO.2.29Al₂O₃.1.36SiO₂.0.06BaF₂:0.07Ce,0.02Eu 0.47Y₂O₃Gd₂O₃.SrO.2.23Al₂O₃.1.38SiO₂.0.12LiF:0.12Ce,0.02Eu 0.47Nd₂O₃Gd₂O₃.SrO.2.22Al₂O₃.1.4SiO₂.0.12LiCl:0.02Ce,0.11Eu 0.44Y₂O₃Gd₂O₃.SrO.2.21Al₂O₃.1.42SiO₂.0.12NaF:0.02Ce,0.02Eu 0.44Y₂O₃Gd₂O₃.SrO.2.2Al₂O₃.1.44SiO₂.0.12NaCl:0.08Ce,0.08Eu 0.41Y₂O₃Gd₂O₃.SrO.2.19Al₂O₃.1.43SiO₂.0.12KF:0.07Ce,0.01Eu 0.41Y₂O₃Gd₂O₃.SrO.2.42Al₂O₃.1.18SiO₂.0.12KCl:0.01Ce,0.03Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.19Al₂O₃.1.46SiO₂.0.06MgF₂:0.08Ce,0.10Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.18Al₂O₃.1.48SiO₂.0.06MgCl₂:0.1Ce,0.1Eu,0.1Tb 0.35Y₂O₃.Gd₂O₃.SrO.1.46Al₂O₃.1.96SiO₂.0.06CaF₂:0.16Ce 0.35Pr₂O₃.Gd₂O₃.SrO.2.17Al₂O₃.1.5SiO₂.0.06CaCl₂:0.12Ce,0.12Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.12Al₂O₃.1.6SiO₂.0.06SrF₂:0.12Ce,0.10Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.07Al₂O₃.1.7SiO₂.0.06SrCl₂:0.08Ce,0.12Eu 0.29Y₂O₃.Gd₂O₃.SrO.2.02Al₂O₃.1.8SiO₂.0.06BaF₂:0.06Ce,0.10Eu and 0.29Nd₂O₃.Gd₂O₃.SrO.1.97Al₂O₃.1.9SiO₂.0.06BaCl₂:0.08Ce,0.10Eu.
 2. A method of producing a phosphor, comprising: weighing elementary substance or compounds or salts of Ln, M, M′, halide of A, and compounds or salts of R and Si as raw materials with weights that are based on the stoichiometric ratio, and adding an excess quantity of SiO₂ and/or AX_(e) as flux into the raw materials, then mixing and grinding to form a mixture; baking the mixture at high temperature under reducing atmosphere; and carrying out a post-treatment of the baked product to obtain the phosphor, wherein the phosphor is represented by a general formula of: aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm; M is at least one metal element selected from a group consisting of Ca, Sr, and Ba; M′ is at least one metal element selected from Al and Ga; A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba; X is at least one element selected from F and Cl; R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn; 0.01≦a≦2; 0.35≦b≦4; 0.01≦c≦1; 0.01≦d≦0.3; 0.01≦f≦3; and 0.65≦e≦2.4, wherein the phosphor is a member from the group consisting of: 1.47Y₂O₃.BaO.2.48Al₂O₃.1.03SiO₂.0.03BaF₂:0.03Ce,0.01Eu 1.47Y₂O₃.BaO.2.47Al₂O₃.1.03SiO₂.0.06BaF₂:0.04Ce,0.03Eu Y₂O₃.0.48Sm₂O₃.BaO.2.45Al₂O₃.1.09SiO₂.0.06BaF₂:0.03Ce,0.04Eu La₂O₃.0.22Gd₂O₃.0.25Sm₂O₃.BaO.2.44Al₂O₃.1.12SiO₂.0.06BaF₂:0.06Ce,0.01Eu,0.001Tb 2.0Y₂O₃.BaO.1.0Al₂O₃.0.05Ga₂O₃.2.5SiO₂.0.36BaF₂:0.07Ce,0.03Eu,0.001Tb 1.91Y₂O₃.BaO.2.01Al₂O₃.1.06SiO₂.0.1LiF:0.09Ce,0.02Eu,0.001Tb 1.34Pr₂O₃.BaO.2.5Al₂O₃.1.09SiO₂.0.16LiCl:0.01Ce,0.08Eu,0.002Tb 0.818Y₂O₃.BaO.3.0Al₂O₃.1.12SiO₂.0.2NaF:0.1Ce,0.04Eu,0.003Tb 0.297Y₂O₃.BaO.3.5Al₂O₃.1.15SiO₂.0.2NaCl:0.12Ce,0.02Eu,0.004Tb 0.01Y₂O₃.BaO.4.0Al₂O₃.0.01SiO₂.0.918KF:0.02Ce,0.1Eu,0.001Tb 1.473Nd₂O₃.BaO.2.79Al₂O₃.0.05SiO₂.0.37KCl:0.02Ce,0.11Eu,0.002Tb 1.471Y₂O₃.BaO.2.81Al₂O₃.0.1SiO₂.0.28MgF₂:0.1Ce,0.12Eu,0.003Mn 1.472Y₂O₃.BaO.2.61Al₂O₃.0.5SiO₂.0.28MgCl₂:0.13Ce,0.01Eu,0.001 Mn 1.482Y₂O₃.BaO.2.215Al₂O₃.1.0SiO₂.0.57CaF₂:0.01Ce,0.12Eu,0.004Mn 1.133Ho₂O₃.BaO.2.2Al₂O₃.2.0SiO₂.0.3CaCl₂:0.1Ce,0.02Eu,0.001Tb 0.8Y₂O₃.BaO.0.42Al₂O₃.3.0SiO₂.0.16SrF₂:0.01Ce,0.1Eu,0.003Tb 1.47Y₂O₃.BaO.2.42Al₂O₃SiO₂.0.16SrCl₂:0.1Ce,0.04Eu Yb₂O₃.0.47Gd₂O₃.BaO.2.24Al₂O₃.1.36SiO₂.0.16LiF:0.13Ce,0.01Eu Y₂O₃.0.44Gd₂O₃.BaO.2.25Al₂O₃.1.39SiO₂.0.16LiCl:0.08Ce,0.09Eu Y₂O₃.0.44Gd₂O₃.BaO.2.21Al₂O₃.1.42SiO₂.0.16NaF:0.09Ce,0.02Eu Y₂O₃.0.41Gd₂O₃.BaO.2.195Al₂O₃.1.45SiO₂.0.16NaCl:0.15Ce,0.13Eu Y₂O₃.0.41Gd₂O₃.BaO.2.18Al₂O₃.1.48SiO₂.0.16KF:0.01Ce,0.01Eu Y₂O₃.0.38Gd₂O₃.CaO.2.42Al₂O₃.1.48SiO₂.0.16KCl:0.03Ce,0.03Eu Y₂O₃.0.38Gd₂O₃.CaO.2.165Al₂O₃.1.51SiO₂.0.16MgF₂:0.08Ce,0.002Tb Y₂O₃.0.35Sc₂O₃.CaO.2.15Al₂O₃.1.54SiO₂.0.16MgCl₂:0.02Ce,0.005Tb Y₂O₃.0.35Gd₂O₃.CaO.2.3Al₂O₃.1.12SiO₂.0.16CaF₂:0.04Ce,0.001Tb Y₂O₃.0.32Gd₂O₃.CaO.2.135Al₂O₃.1.57SiO₂.0.16CaCl₂:0.07Ce,0.08Eu Y₂O₃.0.32La₂O₃.CaO.2.12Al₂O₃.1.6SiO₂.0.16SrF₂:0.02Ce,0.12Eu Y₂O₃.0.29Gd₂O₃CaO.2.105Al₂O₃.1.63SiO₂.0.16SrCl₂:0.14Ce,0.02Eu Y₂O₃.0.29Pr₂O₃CaO.2.09Al₂O₃.1.66SiO₂.0.16BaCl₂:0.02Ce,0.02Eu Y₂O₃.0.26Sm₂O₃.CaO.2.125Al₂O₃.1.74SiO₂.0.01LiF:0.06Ce,0.06Eu Y₂O₃.0.26Sm₂O₃.CaO.2.11Al₂O₃.1.75SiO₂.0.03LiCl:0.09Ce,0.08Eu Y₂O₃.0.23Sm₂O₃.CaO.2.095Al₂O₃.1.75SiO₂.0.06NaF:0.06Ce,0.07Eu Y₂O₃.0.23Sm₂O₃.CaO.2.08Al₂O₃.1.74SiO₂.0.1NaCl:0.05Ce,0.08Eu Y₂O₃.0.2Sm₂O₃.CaO.2.065Al₂O₃.1.67SiO₂.0.2KF:0.16Ce,0.13Eu Y₂O₃.0.2Sm₂O₃.CaO.2.05Al₂O₃.1.6SiO₂.0.3KCl:0.15Ce,0.13Eu Y₂O₃.0.47Sm₂O₃.CaO.2.23Al₂O₃.0.9SiO₂.0.4MgF₂:0.13Ce,0.1Eu Y₂O₃.0.47Nd₂O₃.CaO.2.035Al₂O₃.1.43SiO₂.0.5MgCl₂:0.04Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.02Al₂O₃.1.36SiO₂.0.6CaF₂:0.02Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.2.005Al₂O₃.1.29SiO₂.0.7CaCl₂:0.12Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.1.99Al₂O₃.1.22SiO₂.0.8SrF₂:0.13Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.46Al₂O₃.0.18SiO₂.0.9SrCl₂:0.14Ce,0.05Eu Y₂O₃.0.47Ho₂O₃.CaO.2.45Al₂O₃.0.1SiO₂.1.0BaCl₂:0.06Ce,0.06Eu 1.47Y₂O₃.CaO.2.39Al₂O₃.0.05Ga₂O₃.1.08SiO₂.0.1LiF:0.08Ce,0.05Eu 0.01Y₂O₃CaO.3.84Al₂O₃.0.05Ga₂O₃.1.00SiO₂.0.2LiCl:0.11Ce,0.02Eu 0.05Yb₂O₃CaO.3.36Al₂O₃.0.05Ga₂O₃.1.3SiO₂.0.3NaF:0.1Ce,0.05Eu 0.1Y₂O₃CaO.3.74Al₂O₃.0.05Ga₂O₃.0.82SiO₂.0.4NaCl:0.1Ce,0.03Eu 0.5Y₂O₃CaO.3.33Al₂O₃.0.05Ga₂O₃.0.74SiO₂.0.5KF:0.09Ce,0.02Eu 1.0Y₂O₃CaO.2.82Al₂O₃.0.05Ga₂O₃.0.66SiO₂.0.6KCl:0.08Ce 2.0Y₂O₃CaO.1.81Al₂O₃.0.05Ga₂O₃.0.55SiO₂.0.7MgF₂:0.1Eu 0.01Sc₂O₃.SrO.3.79Al₂O₃.0.05Ga₂O₃.0.44SiO₂.0.8MgCl₂:0.007Ce,0.01Eu 0.05Y₂O₃.SrO.3.74Al₂O₃.0.05Ga₂O₃.0.36SiO₂.0.9CaF₂:0.06Ce,0.04Eu 0.1Y₂O₃.SrO.3.68Al₂O₃.0.05Ga₂O₃.0.28SiO₂.1.0CaCl₂:0.06Ce,0.03Eu 0.5Y₂O₃.SrO.3.27Al₂O₃.0.05Ga₂O₃.1.2SiO₂.0.1SrF₂:0.007Ce,0.04Eu 1.0La₂O₃.SrO.2.76Al₂O₃.0.05Ga₂O₃.1.12SiO₂.0.2SrCl₂:0.09Ce,0.03Eu 2.0Y₂O₃.SrO.1.75Al₂O₃.0.05Ga₂O₃.1.04SiO₂.0.3BaCl₂:0.1Ce,0.1Eu 0.47Pr₂O₃.0.5Gd₂O₃.0.5Sm₂O₃.SrO.2.3Al₂O₃.1.34SiO₂.0.06BaF₂:0.1Ce,0.11Eu 0.47Y₂O₃Gd₂O₃.SrO.2.29Al₂O₃.1.36SiO₂.0.06BaF₂:0.07Ce,0.02Eu 0.47Y₂O₃Gd₂O₃.SrO.2.23Al₂O₃.1.38SiO₂.0.12LiF:0.12Ce,0.02Eu 0.47Nd₂O₃Gd₂O₃.SrO.2.22Al₂O₃.1.4SiO₂.0.12LiCl:0.02Ce,0.11Eu 0.44Y₂O₃Gd₂O₃.SrO.2.21Al₂O₃.1.42SiO₂.0.12NaF:0.02Ce,0.02Eu 0.44Y₂O₃Gd₂O₃.SrO.2.2Al₂O₃.1.44SiO₂.0.12NaCl:0.08Ce,0.08Eu 0.41Y₂O₃Gd₂O₃.SrO.2.19Al₂O₃.1.43SiO₂.0.12KF:0.07Ce,0.01Eu 0.41Y₂O₃Gd₂O₃.SrO.2.42Al₂O₃.1.18SiO₂.0.12KCl:0.01Ce,0.03Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.19Al₂O₃.1.46SiO₂.0.06MgF₂:0.08Ce,0.10Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.18Al₂O₃.1.48SiO₂.0.06MgCl₂:0.1Ce,0.1Eu,0.1Tb 0.35Y₂O₃.Gd₂O₃.SrO.1.46Al₂O₃.1.96SiO₂.0.06CaF₂:0.16Ce 0.35Pr₂O₃.Gd₂O₃.SrO.2.17Al₂O₃.1.5SiO₂.0.06CaCl₂:0.12Ce,0.12Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.12Al₂O₃.1.6SiO₂.0.06SrF₂:0.12Ce,0.10Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.07Al₂O₃.1.7SiO₂.0.06SrCl₂:0.08Ce,0.12Eu 0.29Y₂O₃.Gd₂O₃.SrO.2.02Al₂O₃.1.8SiO₂.0.06BaF₂:0.06Ce,0.10Eu and 0.29Nd₂O₃.Gd₂O₃.SrO.1.97Al₂O₃.1.9SiO₂.0.06BaCl₂:0.08Ce,0.10Eu.
 3. The method according to claim 2, wherein the compounds of Ln, M, M′, A, R and Si are selected from the group consisting of corresponding oxide, hydroxide, carbonate, nitrate, and organic salt.
 4. The method according to claim 2, wherein the amount of flux is in a range between 0.001% to 20% by weight of the total phosphor.
 5. The method according to claim 2, wherein baking is carried out at least two times.
 6. The method according to claim 5, wherein the temperature of baking is at a range between 500° C. to 1600° C.
 7. The method according to claim 4 or 6, wherein each baking operation should last from 0.5 h to 15 h.
 8. The method according to claim 2, wherein the post-treatment includes grinding, air flow crushing, washing, sifting, drying and grading.
 9. The method according to claim 8, wherein the washing step in the post-treatment can be carried out using acid solution, alkali solution or water.
 10. The method according to claim 8, wherein the grading step in the post-treatment is carried out with at least one method selected from a group consisting of sedimentation method, sieving method, hydraulic classification and air flow grading.
 11. A light emitting device comprising: a phosphor; and a semiconductor light emitting element capable of emitting a light in the range from ultraviolet light to visible light, wherein the phosphor is represented by a general formula of: aLn₂O₃.MO.bM′₂O₃ .fSiO₂ .cAX_(e) :dR, wherein Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm; M is at least one metal element selected from a group consisting of Ca, Sr and Ba; M′ is at least one metal element selected from Al and Ga; A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba; X is at least one element selected from F and Cl; R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn; 0.01≦a≦2; 0.35≦b≦4; 0.01≦c≦1; 0.01≦d≦0.3; 0.01≦f≦3; and 0.6≦e≦2.4 wherein the phosphor is a member selected from the group consisting of: 1.47Y₂O₃.BaO.2.48Al₂O₃.1.03SiO₂.0.03BaF₂:0.03Ce,0.01Eu 1.47Y₂O₃.BaO.2.47Al₂O₃.1.03SiO₂.0.06BaF₂:0.04Ce,0.03Eu Y₂O₃.0.48Sm₂O₃.BaO.2.45Al₂O₃.1.09SiO₂.0.06BaF₂:0.03Ce,0.04Eu La₂O₃.0.22Gd₂O₃.0.25Sm₂O₃.BaO.2.44Al₂O₃.1.12SiO₂.0.06BaF₂:0.06Ce,0.01Eu,0.001Tb 2.0Y₂O₃.BaO.1.0Al₂O₃.0.05Ga₂O₃.2.5SiO₂.0.36BaF₂:0.07Ce,0.03Eu,0.001Tb 1.91Y₂O₃.BaO.2.01Al₂O₃.1.06SiO₂.0.1LiF:0.09Ce,0.02Eu,0.001Tb 1.34Pr₂O₃.BaO.2.5Al₂O₃.1.09SiO₂.0.16LiCl:0.01Ce,0.08Eu,0.002Tb 0.818Y₂O₃.BaO.3.0Al₂O₃.1.12SiO₂.0.2NaF:0.1Ce,0.04Eu,0.003Tb 0.297Y₂O₃.BaO.3.5Al₂O₃.1.15SiO₂.0.2NaCl:0.12Ce,0.02Eu,0.004Tb 0.01Y₂O₃.BaO.4.0Al₂O₃.0.01SiO₂.0.918KF:0.02Ce,0.1Eu,0.001Tb 1.473Nd₂O₃.BaO.2.79Al₂O₃.0.05SiO₂.0.37KCl:0.02Ce,0.11Eu,0.002Tb 1.471Y₂O₃.BaO.2.81Al₂O₃.0.1SiO₂.0.28MgF₂:0.1Ce,0.12Eu,0.003Mn 1.472Y₂O₃.BaO.2.61Al₂O₃.0.5SiO₂.0.28MgCl₂:0.13Ce,0.01Eu,0.001 Mn 1.482Y₂O₃.BaO.2.215Al₂O₃.1.0SiO₂.0.57CaF₂:0.01Ce,0.12Eu,0.004Mn 1.133Ho₂O₃.BaO.2.2Al₂O₃.2.0SiO₂.0.3CaCl₂:0.1Ce,0.02Eu,0.001Tb 0.8Y₂O₃.BaO.0.42Al₂O₃.3.0SiO₂.0.16SrF₂:0.01Ce,0.1Eu,0.003Tb 1.47Y₂O₃.BaO.2.42Al₂O₃SiO₂.0.16SrCl₂:0.1Ce,0.04Eu Yb₂O₃.0.47Gd₂O₃.BaO.2.24Al₂O₃.1.36SiO₂.0.16LiF:0.13Ce,0.01Eu Y₂O₃.0.44Gd₂O₃.BaO.2.25Al₂O₃.1.39SiO₂.0.16LiCl:0.08Ce,0.09Eu Y₂O₃.0.44Gd₂O₃.BaO.2.21Al₂O₃.1.42SiO₂.0.16NaF:0.09Ce,0.02Eu Y₂O₃.0.41Gd₂O₃.BaO.2.195Al₂O₃.1.45SiO₂.0.16NaCl:0.15Ce,0.13Eu Y₂O₃.0.41Gd₂O₃.BaO.2.18Al₂O₃.1.48SiO₂.0.16KF:0.01Ce,0.01Eu Y₂O₃.0.38Gd₂O₃.CaO.2.42Al₂O₃.1.48SiO₂.0.16KCl:0.03Ce,0.03Eu Y₂O₃.0.38Gd₂O₃.CaO.2.165Al₂O₃.1.51SiO₂.0.16MgF₂:0.08Ce,0.002Tb Y₂O₃.0.35Sc₂O₃.CaO.2.15Al₂O₃.1.54SiO₂.0.16MgCl₂:0.02Ce,0.005Tb Y₂O₃.0.35Gd₂O₃.CaO.2.3Al₂O₃.1.12SiO₂.0.16CaF₂:0.04Ce,0.001Tb Y₂O₃.0.32Gd₂O₃.CaO.2.135Al₂O₃.1.57SiO₂.0.16CaCl₂:0.07Ce,0.08Eu Y₂O₃.0.32La₂O₃.CaO.2.12Al₂O₃.1.6SiO₂.0.16SrF₂:0.02Ce,0.12Eu Y₂O₃.0.29Gd₂O₃CaO.2.105Al₂O₃.1.63SiO₂.0.16SrCl₂:0.14Ce,0.02Eu Y₂O₃.0.29Pr₂O₃CaO.2.09Al₂O₃.1.66SiO₂.0.16BaCl₂:0.02Ce,0.02Eu Y₂O₃.0.26Sm₂O₃.CaO.2.125Al₂O₃.1.74SiO₂.0.01LiF:0.06Ce,0.06Eu Y₂O₃.0.26Sm₂O₃.CaO.2.11Al₂O₃.1.75SiO₂.0.03LiCl:0.09Ce,0.08Eu Y₂O₃.0.23Sm₂O₃.CaO.2.095Al₂O₃.1.75SiO₂.0.06NaF:0.06Ce,0.07Eu Y₂O₃.0.23Sm₂O₃.CaO.2.08Al₂O₃.1.74SiO₂.0.1NaCl:0.05Ce,0.08Eu Y₂O₃.0.2Sm₂O₃.CaO.2.065Al₂O₃.1.67SiO₂.0.2KF:0.16Ce,0.13Eu Y₂O₃.0.2Sm₂O₃.CaO.2.05Al₂O₃.1.6SiO₂.0.3KCl:0.15Ce,0.13Eu Y₂O₃.0.47Sm₂O₃.CaO.2.23Al₂O₃.0.9SiO₂.0.4MgF₂:0.13Ce,0.1Eu Y₂O₃.0.47Nd₂O₃.CaO.2.035Al₂O₃.1.43SiO₂.0.5MgCl₂:0.04Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.02Al₂O₃.1.36SiO₂.0.6CaF₂:0.02Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.2.005Al₂O₃.1.29SiO₂.0.7CaCl₂:0.12Ce,0.03Eu Y₂O₃.0.47Sm₂O₃.CaO.1.99Al₂O₃.1.22SiO₂.0.8SrF₂:0.13Ce,0.04Eu Y₂O₃.0.47Sm₂O₃.CaO.2.46Al₂O₃.0.18SiO₂.0.9SrCl₂:0.14Ce,0.05Eu Y₂O₃.0.47Ho₂O₃.CaO.2.45Al₂O₃.0.1SiO₂.1.0BaCl₂:0.06Ce,0.06Eu 1.47Y₂O₃.CaO.2.39Al₂O₃.0.05Ga₂O₃.1.08SiO₂.0.1LiF:0.08Ce,0.05Eu 0.01Y₂O₃CaO.3.84Al₂O₃.0.05Ga₂O₃.1.00SiO₂.0.2LiCl:0.11Ce,0.02Eu 0.05Yb₂O₃CaO.3.36Al₂O₃.0.05Ga₂O₃.1.3SiO₂.0.3NaF:0.1Ce,0.05Eu 0.1Y₂O₃CaO.3.74Al₂O₃.0.05Ga₂O₃.0.82SiO₂.0.4NaCl:0.1Ce,0.03Eu 0.5Y₂O₃CaO.3.33Al₂O₃.0.05Ga₂O₃.0.74SiO₂.0.5KF:0.09Ce,0.02Eu 1.0Y₂O₃CaO.2.82Al₂O₃.0.05Ga₂O₃.0.66SiO₂.0.6KCl:0.08Ce 2.0Y₂O₃CaO.1.81Al₂O₃.0.05Ga₂O₃.0.55SiO₂.0.7MgF₂:0.1Eu 0.01Sc₂O₃.SrO.3.79Al₂O₃.0.05Ga₂O₃.0.44SiO₂.0.8MgCl₂:0.007Ce,0.01Eu 0.05Y₂O₃.SrO.3.74Al₂O₃.0.05Ga₂O₃.0.36SiO₂.0.9CaF₂:0.06Ce,0.04Eu 0.1Y₂O₃.SrO.3.68Al₂O₃.0.05Ga₂O₃.0.28SiO₂.1.0CaCl₂:0.06Ce,0.03Eu 0.5Y₂O₃.SrO.3.27Al₂O₃.0.05Ga₂O₃.1.2SiO₂.0.1SrF₂:0.007Ce,0.04Eu 1.0La₂O₃.SrO.2.76Al₂O₃.0.05Ga₂O₃.1.12SiO₂.0.2SrCl₂:0.09Ce,0.03Eu 2.0Y₂O₃.SrO.1.75Al₂O₃.0.05Ga₂O₃.1.04SiO₂.0.3BaCl₂:0.1Ce,0.1Eu 0.47Pr₂O₃.0.5Gd₂O₃.0.5Sm₂O₃.SrO.2.3Al₂O₃.1.34SiO₂.0.06BaF₂:0.1Ce,0.11Eu 0.47Y₂O₃Gd₂O₃.SrO.2.29Al₂O₃.1.36SiO₂.0.06BaF₂:0.07Ce,0.02Eu 0.47Y₂O₃Gd₂O₃.SrO.2.23Al₂O₃.1.38SiO₂.0.12LiF:0.12Ce,0.02Eu 0.47Nd₂O₃Gd₂O₃.SrO.2.22Al₂O₃.1.4SiO₂.0.12LiCl:0.02Ce,0.11Eu 0.44Y₂O₃Gd₂O₃.SrO.2.21Al₂O₃.1.42SiO₂.0.12NaF:0.02Ce,0.02Eu 0.44Y₂O₃Gd₂O₃.SrO.2.2Al₂O₃.1.44SiO₂.0.12NaCl:0.08Ce,0.08Eu 0.41Y₂O₃Gd₂O₃.SrO.2.19Al₂O₃.1.43SiO₂.0.12KF:0.07Ce,0.01Eu 0.41Y₂O₃Gd₂O₃.SrO.2.42Al₂O₃.1.18SiO₂.0.12KCl:0.01Ce,0.03Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.19Al₂O₃.1.46SiO₂.0.06MgF₂:0.08Ce,0.10Eu 0.38Y₂O₃.Gd₂O₃.SrO.2.18Al₂O₃.1.48SiO₂.0.06MgCl₂:0.1Ce,0.1Eu,0.1Tb 0.35Y₂O₃.Gd₂O₃.SrO.1.46Al₂O₃.1.96SiO₂.0.06CaF₂:0.16Ce 0.35Pr₂O₃.Gd₂O₃.SrO.2.17Al₂O₃.1.5SiO₂.0.06CaCl₂:0.12Ce,0.12Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.12Al₂O₃.1.6SiO₂.0.06SrF₂:0.12Ce,0.10Eu 0.32Y₂O₃.Gd₂O₃.SrO.2.07Al₂O₃.1.7SiO₂.0.06SrCl₂:0.08Ce,0.12Eu 0.29Y₂O₃.Gd₂O₃.SrO.2.02Al₂O₃.1.8SiO₂.0.06BaF₂:0.06Ce,0.10Eu and 0.29Nd₂O₃.Gd₂O₃.SrO.1.97Al₂O₃.1.9SiO₂.0.06BaCl₂:0.08Ce,0.10Eu. 